Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives
Identifieur interne : 003194 ( Istex/Corpus ); précédent : 003193; suivant : 003195Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives
Auteurs : Pietro Diversi ; Marco Fontani ; Melania Fuligni ; Franco Laschi ; Simona Matteoni ; Calogero Pinzino ; Piero ZanelloSource :
- Journal of Organometallic Chemistry [ 0022-328X ] ; 2001.
English descriptors
Abstract
The electrochemical behaviour of the ruthenium(II) alkyl complexes [Ru(Me)Cp*(L)2] (Cp*=η5-C5Me5; L=PMe3 2a, PMe2Ph 2b), [Ru(CH2CMe3)Cp*(PMe3)2] (3a), and the related [Ru(Me)Cp(PPh3)2] (4d) (Cp=η5-C5H5) in CH2Cl2 involves a one-electron process, yielding the corresponding ruthenium(III) paramagnetic cations, as shown by coupled electrochemical–EPR studies. Compounds 2–4 are oxidised by [FeCp2]+ in benzene to unidentified paramagnetic products which may decompose giving the corresponding alkane. The Cp* compounds react with NOBF4 affording the monocationic alkylnitrosyl derivatives [Ru(R)Cp*(NO)(L)]BF4 (R=Me; L=PMe3 7a, PMe2Ph 7b. R=CH2CMe3; L=PMe3) and, when in excess of NO+, the ruthenium(II) dicationic complexes [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). The chloro complexes [Ru(Cl)Cp*(L)2] (L=PMe3 1a, PMe2Ph 1b, PPh3 1d) react analogously with NO+ to give [Ru(Cl)Cp*(NO)(L)]BF4 (L=PMe3 6a, PMe2Ph 6b, PPh3 6d) and [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). In contrast [Ru(Me)Cp(PPh3)2] gives only [Ru(Me)Cp(NO)(PPh3)]BF4. EPR spectroscopy suggests that these nitrosylation reactions are also oxidative in character proceeding through ruthenium(III) intermediates.
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DOI: 10.1016/S0022-328X(01)00680-5
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<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives</title><author><name sortKey="Diversi, Pietro" sort="Diversi, Pietro" uniqKey="Diversi P" first="Pietro" last="Diversi">Pietro Diversi</name><affiliation><mods:affiliation>E-mail: div@dcci.unipi.it</mods:affiliation></affiliation><affiliation><mods:affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</mods:affiliation></affiliation></author><author><name sortKey="Fontani, Marco" sort="Fontani, Marco" uniqKey="Fontani M" first="Marco" last="Fontani">Marco Fontani</name><affiliation><mods:affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</mods:affiliation></affiliation></author><author><name sortKey="Fuligni, Melania" sort="Fuligni, Melania" uniqKey="Fuligni M" first="Melania" last="Fuligni">Melania Fuligni</name><affiliation><mods:affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</mods:affiliation></affiliation></author><author><name sortKey="Laschi, Franco" sort="Laschi, Franco" uniqKey="Laschi F" first="Franco" last="Laschi">Franco Laschi</name><affiliation><mods:affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</mods:affiliation></affiliation></author><author><name sortKey="Matteoni, Simona" sort="Matteoni, Simona" uniqKey="Matteoni S" first="Simona" last="Matteoni">Simona Matteoni</name><affiliation><mods:affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</mods:affiliation></affiliation></author><author><name sortKey="Pinzino, Calogero" sort="Pinzino, Calogero" uniqKey="Pinzino C" first="Calogero" last="Pinzino">Calogero 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reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives</title><author><name sortKey="Diversi, Pietro" sort="Diversi, Pietro" uniqKey="Diversi P" first="Pietro" last="Diversi">Pietro Diversi</name><affiliation><mods:affiliation>E-mail: div@dcci.unipi.it</mods:affiliation></affiliation><affiliation><mods:affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</mods:affiliation></affiliation></author><author><name sortKey="Fontani, Marco" sort="Fontani, Marco" uniqKey="Fontani M" first="Marco" last="Fontani">Marco Fontani</name><affiliation><mods:affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</mods:affiliation></affiliation></author><author><name sortKey="Fuligni, Melania" sort="Fuligni, Melania" uniqKey="Fuligni M" first="Melania" last="Fuligni">Melania Fuligni</name><affiliation><mods:affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</mods:affiliation></affiliation></author><author><name sortKey="Laschi, Franco" sort="Laschi, Franco" uniqKey="Laschi F" first="Franco" last="Laschi">Franco Laschi</name><affiliation><mods:affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</mods:affiliation></affiliation></author><author><name sortKey="Matteoni, Simona" sort="Matteoni, Simona" uniqKey="Matteoni S" first="Simona" last="Matteoni">Simona Matteoni</name><affiliation><mods:affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</mods:affiliation></affiliation></author><author><name sortKey="Pinzino, Calogero" sort="Pinzino, Calogero" uniqKey="Pinzino C" first="Calogero" last="Pinzino">Calogero Pinzino</name><affiliation><mods:affiliation>Istituto di Chimica Quantistica e Energetica Molecolare del CNR, Area della ricerca di Pisa, Via Alfieri 1, Ghezzano, 56010 Pisa, Italy</mods:affiliation></affiliation></author><author><name sortKey="Zanello, Piero" sort="Zanello, Piero" uniqKey="Zanello P" first="Piero" last="Zanello">Piero Zanello</name><affiliation><mods:affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Journal of Organometallic Chemistry</title><title level="j" type="abbrev">JOM</title><idno type="ISSN">0022-328X</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="2001">2001</date><biblScope unit="volume">626</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="145">145</biblScope><biblScope unit="page" to="156">156</biblScope></imprint><idno type="ISSN">0022-328X</idno></series><idno type="istex">B48948A1DE34D44EA1A0583D281A8AC18F4FAC15</idno><idno type="DOI">10.1016/S0022-328X(01)00680-5</idno><idno type="PII">S0022-328X(01)00680-5</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0022-328X</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>EPR spectroscopy</term><term>Electrochemistry</term><term>Nitrosyls</term><term>Rutheniumcarbon bond cleavage</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The electrochemical behaviour of the ruthenium(II) alkyl complexes [Ru(Me)Cp*(L)2] (Cp*=η5-C5Me5; L=PMe3 2a, PMe2Ph 2b), [Ru(CH2CMe3)Cp*(PMe3)2] (3a), and the related [Ru(Me)Cp(PPh3)2] (4d) (Cp=η5-C5H5) in CH2Cl2 involves a one-electron process, yielding the corresponding ruthenium(III) paramagnetic cations, as shown by coupled electrochemical–EPR studies. Compounds 2–4 are oxidised by [FeCp2]+ in benzene to unidentified paramagnetic products which may decompose giving the corresponding alkane. The Cp* compounds react with NOBF4 affording the monocationic alkylnitrosyl derivatives [Ru(R)Cp*(NO)(L)]BF4 (R=Me; L=PMe3 7a, PMe2Ph 7b. R=CH2CMe3; L=PMe3) and, when in excess of NO+, the ruthenium(II) dicationic complexes [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). The chloro complexes [Ru(Cl)Cp*(L)2] (L=PMe3 1a, PMe2Ph 1b, PPh3 1d) react analogously with NO+ to give [Ru(Cl)Cp*(NO)(L)]BF4 (L=PMe3 6a, PMe2Ph 6b, PPh3 6d) and [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). In contrast [Ru(Me)Cp(PPh3)2] gives only [Ru(Me)Cp(NO)(PPh3)]BF4. EPR spectroscopy suggests that these nitrosylation reactions are also oxidative in character proceeding through ruthenium(III) intermediates.</div></front></TEI><istex><corpusName>elsevier</corpusName><author><json:item><name>Pietro Diversi</name><affiliations><json:string>E-mail: div@dcci.unipi.it</json:string><json:string>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</json:string></affiliations></json:item><json:item><name>Marco Fontani</name><affiliations><json:string>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</json:string></affiliations></json:item><json:item><name>Melania Fuligni</name><affiliations><json:string>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</json:string></affiliations></json:item><json:item><name>Franco Laschi</name><affiliations><json:string>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</json:string></affiliations></json:item><json:item><name>Simona Matteoni</name><affiliations><json:string>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</json:string></affiliations></json:item><json:item><name>Calogero Pinzino</name><affiliations><json:string>Istituto di Chimica Quantistica e Energetica Molecolare del CNR, Area della ricerca di Pisa, Via Alfieri 1, Ghezzano, 56010 Pisa, Italy</json:string></affiliations></json:item><json:item><name>Piero Zanello</name><affiliations><json:string>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Nitrosyls</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Rutheniumcarbon bond cleavage</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Electrochemistry</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>EPR spectroscopy</value></json:item></subject><language><json:string>eng</json:string></language><abstract>The electrochemical behaviour of the ruthenium(II) alkyl complexes [Ru(Me)Cp*(L)2] (Cp*=η5-C5Me5; L=PMe3 2a, PMe2Ph 2b), [Ru(CH2CMe3)Cp*(PMe3)2] (3a), and the related [Ru(Me)Cp(PPh3)2] (4d) (Cp=η5-C5H5) in CH2Cl2 involves a one-electron process, yielding the corresponding ruthenium(III) paramagnetic cations, as shown by coupled electrochemical–EPR studies. Compounds 2–4 are oxidised by [FeCp2]+ in benzene to unidentified paramagnetic products which may decompose giving the corresponding alkane. The Cp* compounds react with NOBF4 affording the monocationic alkylnitrosyl derivatives [Ru(R)Cp*(NO)(L)]BF4 (R=Me; L=PMe3 7a, PMe2Ph 7b. R=CH2CMe3; L=PMe3) and, when in excess of NO+, the ruthenium(II) dicationic complexes [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). The chloro complexes [Ru(Cl)Cp*(L)2] (L=PMe3 1a, PMe2Ph 1b, PPh3 1d) react analogously with NO+ to give [Ru(Cl)Cp*(NO)(L)]BF4 (L=PMe3 6a, PMe2Ph 6b, PPh3 6d) and [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). In contrast [Ru(Me)Cp(PPh3)2] gives only [Ru(Me)Cp(NO)(PPh3)]BF4. EPR spectroscopy suggests that these nitrosylation reactions are also oxidative in character proceeding through ruthenium(III) intermediates.</abstract><qualityIndicators><score>6.728</score><pdfVersion>1.2</pdfVersion><pdfPageSize>604 x 789 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>4</keywordCount><abstractCharCount>1185</abstractCharCount><pdfWordCount>7684</pdfWordCount><pdfCharCount>45703</pdfCharCount><pdfPageCount>12</pdfPageCount><abstractWordCount>144</abstractWordCount></qualityIndicators><title>Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives</title><pii><json:string>S0022-328X(01)00680-5</json:string></pii><genre><json:string>research-article</json:string></genre><serie><genre></genre><language><json:string>unknown</json:string></language><title>(Chap. 4)</title></serie><host><volume>626</volume><pii><json:string>S0022-328X(00)X1195-3</json:string></pii><pages><last>156</last><first>145</first></pages><issn><json:string>0022-328X</json:string></issn><issue>1–2</issue><genre><json:string>Journal</json:string></genre><language><json:string>unknown</json:string></language><title>Journal of Organometallic Chemistry</title><publicationDate>2001</publicationDate></host><categories><wos><json:string>CHEMISTRY, INORGANIC & NUCLEAR</json:string><json:string>CHEMISTRY, ORGANIC</json:string></wos></categories><publicationDate>2001</publicationDate><copyrightDate>2001</copyrightDate><doi><json:string>10.1016/S0022-328X(01)00680-5</json:string></doi><id>B48948A1DE34D44EA1A0583D281A8AC18F4FAC15</id><score>1</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/B48948A1DE34D44EA1A0583D281A8AC18F4FAC15/fulltext/pdf</uri></json:item><json:item><original>true</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/B48948A1DE34D44EA1A0583D281A8AC18F4FAC15/fulltext/txt</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/B48948A1DE34D44EA1A0583D281A8AC18F4FAC15/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/B48948A1DE34D44EA1A0583D281A8AC18F4FAC15/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>ELSEVIER</p></availability><date>2001</date></publicationStmt><notesStmt><note type="content">Fig. 1: Cyclic voltammogram recorded at a platinum electrode on CH2Cl2 solution containing 2b (2.4×10−3 dm−3) and [NBu4]PF6 (0.2 dm−3). Temperature=0°C. Scan rate: 0.2 Vs−1.</note><note type="content">Fig. 2: Cyclic voltammogram recorded at a platinum electrode on CH2Cl2 solution containing 3a (1.0×10−3 dm−3) and [NBu4]PF6 (0.2 moldm−3). Temperature=0°C. Scan rate: 0.2 Vs−1.</note><note type="content">Fig. 3: Experimental (upper) and simulated (lower) EPR spectra of 4d+ at 100 K.</note><note type="content">Scheme 1:</note><note type="content">Fig. 4: EPR experimental (upper) and simulated (lower) spectra of the species generated by reaction of [Ru(Cl)Cp*(PMe3)2] (1a) with NOBF4 in CH2Cl2: (a) fluid solution; and (b) frozen solution.</note><note type="content">Scheme 2:</note><note type="content">Fig. 5: EPR experimental (upper) and simulated (lower) spectrum of the species generated by reaction of [Ru(Cl)Cp(PPh3)2] in CH2Cl2 with NOBF4 (frozen solution).</note><note type="content">Scheme 3:</note><note type="content">Table 1: Formal electrode potentials (in V vs. SCE) and peak-to-peak separations (in mV) for the oxidation processes of the Ru(II) complexes under study in CH2Cl2 solution</note><note type="content">Table 2: X-band EPR parameters of the electrogenerated compounds 2b+ and 4d+, recorded at liquid nitrogen temperature (T=100 K)</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives</title><author><persName><forename type="first">Pietro</forename><surname>Diversi</surname></persName><email>div@dcci.unipi.it</email><note type="correspondence"><p>Corresponding author. Tel.: +39-50-918225; fax: +39-50-918260</p></note><affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</affiliation></author><author><persName><forename type="first">Marco</forename><surname>Fontani</surname></persName><affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</affiliation></author><author><persName><forename type="first">Melania</forename><surname>Fuligni</surname></persName><affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</affiliation></author><author><persName><forename type="first">Franco</forename><surname>Laschi</surname></persName><affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</affiliation></author><author><persName><forename type="first">Simona</forename><surname>Matteoni</surname></persName><affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</affiliation></author><author><persName><forename type="first">Calogero</forename><surname>Pinzino</surname></persName><affiliation>Istituto di Chimica Quantistica e Energetica Molecolare del CNR, Area della ricerca di Pisa, Via Alfieri 1, Ghezzano, 56010 Pisa, Italy</affiliation></author><author><persName><forename type="first">Piero</forename><surname>Zanello</surname></persName><affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</affiliation></author></analytic><monogr><title level="j">Journal of Organometallic Chemistry</title><title level="j" type="abbrev">JOM</title><idno type="pISSN">0022-328X</idno><idno type="PII">S0022-328X(00)X1195-3</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="2001"></date><biblScope unit="volume">626</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="145">145</biblScope><biblScope unit="page" to="156">156</biblScope></imprint></monogr><idno type="istex">B48948A1DE34D44EA1A0583D281A8AC18F4FAC15</idno><idno type="DOI">10.1016/S0022-328X(01)00680-5</idno><idno type="PII">S0022-328X(01)00680-5</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2001</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The electrochemical behaviour of the ruthenium(II) alkyl complexes [Ru(Me)Cp*(L)2] (Cp*=η5-C5Me5; L=PMe3 2a, PMe2Ph 2b), [Ru(CH2CMe3)Cp*(PMe3)2] (3a), and the related [Ru(Me)Cp(PPh3)2] (4d) (Cp=η5-C5H5) in CH2Cl2 involves a one-electron process, yielding the corresponding ruthenium(III) paramagnetic cations, as shown by coupled electrochemical–EPR studies. Compounds 2–4 are oxidised by [FeCp2]+ in benzene to unidentified paramagnetic products which may decompose giving the corresponding alkane. The Cp* compounds react with NOBF4 affording the monocationic alkylnitrosyl derivatives [Ru(R)Cp*(NO)(L)]BF4 (R=Me; L=PMe3 7a, PMe2Ph 7b. R=CH2CMe3; L=PMe3) and, when in excess of NO+, the ruthenium(II) dicationic complexes [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). The chloro complexes [Ru(Cl)Cp*(L)2] (L=PMe3 1a, PMe2Ph 1b, PPh3 1d) react analogously with NO+ to give [Ru(Cl)Cp*(NO)(L)]BF4 (L=PMe3 6a, PMe2Ph 6b, PPh3 6d) and [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). In contrast [Ru(Me)Cp(PPh3)2] gives only [Ru(Me)Cp(NO)(PPh3)]BF4. EPR spectroscopy suggests that these nitrosylation reactions are also oxidative in character proceeding through ruthenium(III) intermediates.</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>Keywords</head><item><term>Nitrosyls</term></item><item><term>Rutheniumcarbon bond cleavage</term></item><item><term>Electrochemistry</term></item><item><term>EPR spectroscopy</term></item></list></keywords></textClass></profileDesc><revisionDesc><change when="2001-01-05">Registration</change><change when="2001">Published</change></revisionDesc></teiHeader></istex:fulltextTEI></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier, elements deleted: ce:floats; body; tail"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 4.5.2//EN//XML" URI="art452.dtd" name="istex:docType"><istex:entity SYSTEM="gr1" NDATA="IMAGE" name="gr1"></istex:entity><istex:entity SYSTEM="gr2" NDATA="IMAGE" name="gr2"></istex:entity><istex:entity SYSTEM="gr3" NDATA="IMAGE" name="gr3"></istex:entity><istex:entity SYSTEM="sc1" NDATA="IMAGE" name="sc1"></istex:entity><istex:entity SYSTEM="gr4" NDATA="IMAGE" name="gr4"></istex:entity><istex:entity SYSTEM="sc2" NDATA="IMAGE" name="sc2"></istex:entity><istex:entity SYSTEM="gr5" NDATA="IMAGE" name="gr5"></istex:entity><istex:entity SYSTEM="sc3" NDATA="IMAGE" name="sc3"></istex:entity></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="fla" xml:lang="en"><item-info><jid>JOM</jid><aid>10393</aid><ce:pii>S0022-328X(01)00680-5</ce:pii><ce:doi>10.1016/S0022-328X(01)00680-5</ce:doi><ce:copyright type="full-transfer" year="2001">Elsevier Science B.V.</ce:copyright></item-info><head><ce:title>Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives</ce:title><ce:author-group><ce:author><ce:given-name>Pietro</ce:given-name><ce:surname>Diversi</ce:surname><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref><ce:cross-ref refid="CORR1">*</ce:cross-ref><ce:e-address>div@dcci.unipi.it</ce:e-address></ce:author><ce:author><ce:given-name>Marco</ce:given-name><ce:surname>Fontani</ce:surname><ce:cross-ref refid="AFF2"><ce:sup>b</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Melania</ce:given-name><ce:surname>Fuligni</ce:surname><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Franco</ce:given-name><ce:surname>Laschi</ce:surname><ce:cross-ref refid="AFF2"><ce:sup>b</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Simona</ce:given-name><ce:surname>Matteoni</ce:surname><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Calogero</ce:given-name><ce:surname>Pinzino</ce:surname><ce:cross-ref refid="AFF3"><ce:sup>c</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Piero</ce:given-name><ce:surname>Zanello</ce:surname><ce:cross-ref refid="AFF2"><ce:sup>b</ce:sup></ce:cross-ref></ce:author><ce:affiliation id="AFF1"><ce:label>a</ce:label><ce:textfn>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</ce:textfn></ce:affiliation><ce:affiliation id="AFF2"><ce:label>b</ce:label><ce:textfn>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</ce:textfn></ce:affiliation><ce:affiliation id="AFF3"><ce:label>c</ce:label><ce:textfn>Istituto di Chimica Quantistica e Energetica Molecolare del CNR, Area della ricerca di Pisa, Via Alfieri 1, Ghezzano, 56010 Pisa, Italy</ce:textfn></ce:affiliation><ce:correspondence id="CORR1"><ce:label>*</ce:label><ce:text>Corresponding author. Tel.: +39-50-918225; fax: +39-50-918260</ce:text></ce:correspondence></ce:author-group><ce:date-received day="23" month="10" year="2000"></ce:date-received><ce:date-accepted day="5" month="1" year="2001"></ce:date-accepted><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The electrochemical behaviour of the ruthenium(II) alkyl complexes [Ru(Me)Cp*(L)<ce:inf>2</ce:inf>] (Cp*=η<ce:sup>5</ce:sup>-C<ce:inf>5</ce:inf>Me<ce:inf>5</ce:inf>; L=PMe<ce:inf>3</ce:inf> <ce:bold>2a</ce:bold>, PMe<ce:inf>2</ce:inf>Ph <ce:bold>2b</ce:bold>), [Ru(CH<ce:inf>2</ce:inf>CMe<ce:inf>3</ce:inf>)Cp*(PMe<ce:inf>3</ce:inf>)<ce:inf>2</ce:inf>] (<ce:bold>3a</ce:bold>), and the related [Ru(Me)Cp(PPh<ce:inf>3</ce:inf>)<ce:inf>2</ce:inf>] (<ce:bold>4d</ce:bold>) (Cp=η<ce:sup>5</ce:sup>-C<ce:inf>5</ce:inf>H<ce:inf>5</ce:inf>) in CH<ce:inf>2</ce:inf>Cl<ce:inf>2</ce:inf> involves a one-electron process, yielding the corresponding ruthenium(III) paramagnetic cations, as shown by coupled electrochemical–EPR studies. Compounds <ce:bold>2</ce:bold>–<ce:bold>4</ce:bold> are oxidised by [FeCp<ce:inf>2</ce:inf>]<ce:sup>+</ce:sup> in benzene to unidentified paramagnetic products which may decompose giving the corresponding alkane. The Cp* compounds react with NOBF<ce:inf>4</ce:inf> affording the monocationic alkylnitrosyl derivatives [Ru(R)Cp*(NO)(L)]BF<ce:inf>4</ce:inf> (R=Me; L=PMe<ce:inf>3</ce:inf> <ce:bold>7a</ce:bold>, PMe<ce:inf>2</ce:inf>Ph <ce:bold>7b</ce:bold>. R=CH<ce:inf>2</ce:inf>CMe<ce:inf>3</ce:inf>; L=PMe<ce:inf>3</ce:inf>) and, when in excess of NO<ce:sup>+</ce:sup>, the ruthenium(II) dicationic complexes [RuCp*(NO)(L)<ce:inf>2</ce:inf>](BF<ce:inf>4</ce:inf>)<ce:inf>2</ce:inf> (L=PMe<ce:inf>3</ce:inf> <ce:bold>5a</ce:bold>, PMe<ce:inf>2</ce:inf>Ph <ce:bold>5b</ce:bold>). The chloro complexes [Ru(Cl)Cp*(L)<ce:inf>2</ce:inf>] (L=PMe<ce:inf>3</ce:inf> <ce:bold>1a</ce:bold>, PMe<ce:inf>2</ce:inf>Ph <ce:bold>1b,</ce:bold> PPh<ce:inf>3</ce:inf> <ce:bold>1d</ce:bold>) react analogously with NO<ce:sup>+</ce:sup> to give [Ru(Cl)Cp*(NO)(L)]BF<ce:inf>4</ce:inf> (L=PMe<ce:inf>3</ce:inf> <ce:bold>6a</ce:bold>, PMe<ce:inf>2</ce:inf>Ph <ce:bold>6b,</ce:bold> PPh<ce:inf>3</ce:inf> <ce:bold>6d</ce:bold>) and [RuCp*(NO)(L)<ce:inf>2</ce:inf>](BF<ce:inf>4</ce:inf>)<ce:inf>2</ce:inf> (L=PMe<ce:inf>3</ce:inf> <ce:bold>5a</ce:bold>, PMe<ce:inf>2</ce:inf>Ph <ce:bold>5b</ce:bold>). In contrast [Ru(Me)Cp(PPh<ce:inf>3</ce:inf>)<ce:inf>2</ce:inf>] gives only [Ru(Me)Cp(NO)(PPh<ce:inf>3</ce:inf>)]BF<ce:inf>4</ce:inf>. EPR spectroscopy suggests that these nitrosylation reactions are also oxidative in character proceeding through ruthenium(III) intermediates.</ce:simple-para></ce:abstract-sec></ce:abstract><ce:keywords class="keyword"><ce:section-title>Keywords</ce:section-title><ce:keyword><ce:text>Nitrosyls</ce:text></ce:keyword><ce:keyword><ce:text>Rutheniumcarbon bond cleavage</ce:text></ce:keyword><ce:keyword><ce:text>Electrochemistry</ce:text></ce:keyword><ce:keyword><ce:text>EPR spectroscopy</ce:text></ce:keyword></ce:keywords></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives</title></titleInfo><titleInfo type="alternative" lang="en" contentType="CDATA"><title>Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives</title></titleInfo><name type="personal"><namePart type="given">Pietro</namePart><namePart type="family">Diversi</namePart><affiliation>E-mail: div@dcci.unipi.it</affiliation><affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</affiliation><description>Corresponding author. Tel.: +39-50-918225; fax: +39-50-918260</description><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Marco</namePart><namePart type="family">Fontani</namePart><affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Melania</namePart><namePart type="family">Fuligni</namePart><affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Franco</namePart><namePart type="family">Laschi</namePart><affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Simona</namePart><namePart type="family">Matteoni</namePart><affiliation>Dipartimento di Chimica e Chimica Industriale dell'Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Calogero</namePart><namePart type="family">Pinzino</namePart><affiliation>Istituto di Chimica Quantistica e Energetica Molecolare del CNR, Area della ricerca di Pisa, Via Alfieri 1, Ghezzano, 56010 Pisa, Italy</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Piero</namePart><namePart type="family">Zanello</namePart><affiliation>Dipartimento di Chimica, Università di Siena, Via Aldo Moro, 53100 Siena, Italy</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article"></genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">2001</dateIssued><dateValid encoding="w3cdtf">2001-01-05</dateValid><copyrightDate encoding="w3cdtf">2001</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType></physicalDescription><abstract lang="en">The electrochemical behaviour of the ruthenium(II) alkyl complexes [Ru(Me)Cp*(L)2] (Cp*=η5-C5Me5; L=PMe3 2a, PMe2Ph 2b), [Ru(CH2CMe3)Cp*(PMe3)2] (3a), and the related [Ru(Me)Cp(PPh3)2] (4d) (Cp=η5-C5H5) in CH2Cl2 involves a one-electron process, yielding the corresponding ruthenium(III) paramagnetic cations, as shown by coupled electrochemical–EPR studies. Compounds 2–4 are oxidised by [FeCp2]+ in benzene to unidentified paramagnetic products which may decompose giving the corresponding alkane. The Cp* compounds react with NOBF4 affording the monocationic alkylnitrosyl derivatives [Ru(R)Cp*(NO)(L)]BF4 (R=Me; L=PMe3 7a, PMe2Ph 7b. R=CH2CMe3; L=PMe3) and, when in excess of NO+, the ruthenium(II) dicationic complexes [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). The chloro complexes [Ru(Cl)Cp*(L)2] (L=PMe3 1a, PMe2Ph 1b, PPh3 1d) react analogously with NO+ to give [Ru(Cl)Cp*(NO)(L)]BF4 (L=PMe3 6a, PMe2Ph 6b, PPh3 6d) and [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). In contrast [Ru(Me)Cp(PPh3)2] gives only [Ru(Me)Cp(NO)(PPh3)]BF4. EPR spectroscopy suggests that these nitrosylation reactions are also oxidative in character proceeding through ruthenium(III) intermediates.</abstract><note type="content">Fig. 1: Cyclic voltammogram recorded at a platinum electrode on CH2Cl2 solution containing 2b (2.4×10−3 dm−3) and [NBu4]PF6 (0.2 dm−3). Temperature=0°C. Scan rate: 0.2 Vs−1.</note><note type="content">Fig. 2: Cyclic voltammogram recorded at a platinum electrode on CH2Cl2 solution containing 3a (1.0×10−3 dm−3) and [NBu4]PF6 (0.2 moldm−3). Temperature=0°C. Scan rate: 0.2 Vs−1.</note><note type="content">Fig. 3: Experimental (upper) and simulated (lower) EPR spectra of 4d+ at 100 K.</note><note type="content">Scheme 1: </note><note type="content">Fig. 4: EPR experimental (upper) and simulated (lower) spectra of the species generated by reaction of [Ru(Cl)Cp*(PMe3)2] (1a) with NOBF4 in CH2Cl2: (a) fluid solution; and (b) frozen solution.</note><note type="content">Scheme 2: </note><note type="content">Fig. 5: EPR experimental (upper) and simulated (lower) spectrum of the species generated by reaction of [Ru(Cl)Cp(PPh3)2] in CH2Cl2 with NOBF4 (frozen solution).</note><note type="content">Scheme 3: </note><note type="content">Table 1: Formal electrode potentials (in V vs. SCE) and peak-to-peak separations (in mV) for the oxidation processes of the Ru(II) complexes under study in CH2Cl2 solution</note><note type="content">Table 2: X-band EPR parameters of the electrogenerated compounds 2b+ and 4d+, recorded at liquid nitrogen temperature (T=100 K)</note><subject lang="en"><genre>Keywords</genre><topic>Nitrosyls</topic><topic>Rutheniumcarbon bond cleavage</topic><topic>Electrochemistry</topic><topic>EPR spectroscopy</topic></subject><relatedItem type="host"><titleInfo><title>Journal of Organometallic Chemistry</title></titleInfo><titleInfo type="abbreviated"><title>JOM</title></titleInfo><genre type="Journal">journal</genre><originInfo><dateIssued encoding="w3cdtf">20010430</dateIssued></originInfo><identifier type="ISSN">0022-328X</identifier><identifier type="PII">S0022-328X(00)X1195-3</identifier><part><date>20010430</date><detail type="volume"><number>626</number><caption>vol.</caption></detail><detail type="issue"><number>1–2</number><caption>no.</caption></detail><extent unit="issue pages"><start>1</start><end>272</end></extent><extent unit="pages"><start>145</start><end>156</end></extent></part></relatedItem><identifier type="istex">B48948A1DE34D44EA1A0583D281A8AC18F4FAC15</identifier><identifier type="DOI">10.1016/S0022-328X(01)00680-5</identifier><identifier type="PII">S0022-328X(01)00680-5</identifier><accessCondition type="use and reproduction" contentType="">© 2001Elsevier Science B.V.</accessCondition><recordInfo><recordContentSource>ELSEVIER</recordContentSource><recordOrigin>Elsevier Science B.V., ©2001</recordOrigin></recordInfo></mods></metadata><enrichments><istex:catWosTEI uri="https://api.istex.fr/document/B48948A1DE34D44EA1A0583D281A8AC18F4FAC15/enrichments/catWos"><teiHeader><profileDesc><textClass><classCode scheme="WOS">CHEMISTRY, INORGANIC & NUCLEAR</classCode><classCode scheme="WOS">CHEMISTRY, ORGANIC</classCode></textClass></profileDesc></teiHeader></istex:catWosTEI></enrichments></istex></record>Pour manipuler ce document sous Unix (Dilib)
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